CN104736639A - Polyamide composition, method, and article - Google Patents

Polyamide composition, method, and article Download PDF

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CN104736639A
CN104736639A CN201380055613.9A CN201380055613A CN104736639A CN 104736639 A CN104736639 A CN 104736639A CN 201380055613 A CN201380055613 A CN 201380055613A CN 104736639 A CN104736639 A CN 104736639A
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weight percentage
polymeric amide
poly
phenylene ether
masterbatch
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CN104736639B (en
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约翰内斯·E·福泰因
斯内扎纳·格尔塞夫
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SABIC Global Technologies BV
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SABIC Innovative Plastics IP BV
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    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
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    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres

Abstract

A method of forming a polyamide composition includes melt blending specific amounts of a poly(phenylene ether) masterbatch, a first polyamide, glass fibers, and a flame retardant that includes a metal dialkylphosphinate. The poly(phenylene ether) masterbatch is prepared by melt blending specific amounts of a poly(phenylene ether) and a second polyamide. The method provides a polyamide composition with a desirable balance of flame retardancy, melt flow, heat resistance, and mechanical properties, while reducing the amount of metal dialkylphosphinate required by corresponding compositions without the poly(phenylene ether) masterbatch. A corresponding polyamide composition is described, as are the poly(phenylene ether) masterbatch, and a method of reducing the metal dialkylphosphinate content of a flame retardant polyamide composition.

Description

Daiamid composition, method, and goods
Background technology
Because fluidity of molten, chemical resistant properties, shock resistance and electrical properties that polymeric amide (also referred to as nylon) is good, it is widely used in the application of various Electrical and Electronic.Needs are had to the application of the daiamid composition of the glass-filled of the flame retardant resistance of height, flame retardant additives must be added into composition.Metal dialkyl phosphinates is the preferred fire retardant of polymeric amide at present, but they are expensive and them must be used to provide higher flame retardant resistance with relatively high concentration.Therefore for the metal dialkyl phosphinates reducing high density, substantially maintain flame retardant resistance, fluidity of molten, heat impedance, and there is demand in the daiamid composition of the glass-filled of mechanical property simultaneously.
Summary of the invention
A kind of embodiment is the method forming daiamid composition, the method comprises: based on the weight of daiamid composition, melt blending comprises the component of the following to form daiamid composition: poly-(phenylene ether) masterbatch of 5 to 30 weight percentage, first polymeric amide of 35 to 70 weight percentage, the glass fibre of 15 to 40 weight percentage, and the fire retardant comprising metal dialkyl phosphinates of 10 to 20 weight percentage; Wherein, based on the weight of poly-(phenylene ether) masterbatch, poly-(phenylene ether) masterbatch is the product that melt blending comprises the component of the following: poly-(phenylene ether) of 35 to 97 weight percentage, and the second polymeric amide of 3 to 65 weight percentage.
Other embodiment is the method forming daiamid composition, the method comprises: based on the weight of daiamid composition, melt blending comprises the component of the following to form daiamid composition: poly-(phenylene ether) masterbatch of 5 to 14 weight percentage, 45 to 55 weight percentage comprise polymeric amide-6, first polymeric amide of 6, the glass fibre of 20 to 30 weight percentage, with 12 to 18 weight percentage comprise metal dialkyl phosphinates, melamine polyphosphate, and the fire retardant of zinc borate; Wherein, based on the weight of poly-(phenylene ether) masterbatch, poly-(phenylene ether) masterbatch is the product that melt blending comprises the component of the following: the homopolymer comprising the monomer being selected from the group be made up of the following of 75 to 96.5 weight percentage or poly-(phenylene ether) of multipolymer: 2,6-xylenol, 2,3,6-pseudocuminol, and their combination; Second polymeric amide comprising polymeric amide-6,6 of 3 to 24.5 weight percentage; With poly-(phenylene ether) of 0.5 to 4 weight percentage and the expanding material (compatibilizing agent) of the second polymeric amide; Wherein, based on the gross weight of composition, daiamid composition comprises poly-(phenylene ether) that be less than or equal to 13 weight percentage; And wherein, daiamid composition does not comprise conductive filler material and impact modifier.
Other embodiment is the daiamid composition prepared according to above-described method.
Other embodiment is daiamid composition, comprises the product of melt blending the following: the polymeric amide of 40 to 60 weight percentage; Poly-(phenylene ether) of 3 to 13 weight percentage; 12 to 18 weight percentage comprise metal dialkyl phosphinates, melamine polyphosphate, and the fire retardant of zinc borate; The polymeric amide of 0.1 to 2 weight percentage and the expanding material of poly-(phenylene ether); With the glass fibre of 20 to 40 weight percentage; Wherein, all weight percentage are the gross weights based on daiamid composition.
Other embodiment is the goods of the composition comprising the product comprising melt blending the following: the polymeric amide of 40 to 60 weight percentage; Poly-(phenylene ether) of 3 to 13 weight percentage; 12 to 18 weight percentage comprise metal dialkyl phosphinates, melamine polyphosphate, and the fire retardant of zinc borate; The polymeric amide of 0.1 to 2 weight percentage and the expanding material of poly-(phenylene ether); With the glass fibre of 20 to 40 weight percentage; Wherein, all weight percentage are the gross weights based on daiamid composition.
Other embodiment is the method for the metal dialkyl phosphinates content reducing retardant polyamide composition, comprise: based on the weight of daiamid composition, melt blending comprises the component of the following to form daiamid composition: poly-(phenylene ether) masterbatch of 5 to 30 weight percentage, first polymeric amide of 35 to 70 weight percentage, the glass fibre of 15 to 40 weight percentage, and the fire retardant comprising metal dialkyl phosphinates of 10 to 20 weight percentage; Wherein, based on the weight of poly-(phenylene ether) masterbatch, poly-(phenylene ether) masterbatch is the product that melt blending comprises the component of the following: poly-(phenylene ether) of 35 to 97 weight percentage, and the second polymeric amide of 3 to 65 weight percentage.
Be discussed in more detail below these and other embodiment.
Embodiment
The present inventor has confirmed that the daiamid composition of the glass-filled of the metal dialkyl phosphinates content with minimizing demonstrates desirable flame retardant resistance, fluidity of molten, heat impedance, and mechanical property.Composition can be prepared by utilizing mixing (compounding) method of specific poly-(phenylene ether) masterbatch.Composition has benefited from gathering (phenylene ether) flame retardant synergist effect, avoids using unmanageable poly-(phenylene ether) powder simultaneously.
About flammable performance, in Underwriters Laboratory bulletin 94 " combustibility of plastic material test; UL94 " (Underwriter ' s Laboratory Bulletin 94 " Tests for Flammability ofPlastic Materials; UL 94 ") 20mm Vertical Burning Flame test, under the thickness of sample of 0.8 millimeter, daiamid composition can demonstrate the grade of V-0 or V-1.
About melt flowability, daiamid composition can show the temperature and 1 of use 282 DEG C, 500 seconds -1shearing rate, determine according to ISO 11443:2005, be less than or equal to the melt viscosity of 251 pascals-second.In some embodiments, melt viscosity is 100 to 250 pascals-second, particularly, and 100 to 160 pascals-second.
About hardness performance, daiamid composition can show use 80 millimeters and be multiplied by the rod that 10 millimeters are multiplied by the cross-sectional dimension of 4 millimeters, the bearing stride of 64 millimeters, and each composition three samples, according to the modulus in flexure of at least 7200 MPas that ISO 178:2010 determines at 23 DEG C.In some embodiments, modulus in flexure is 7200 to 9000 MPas, particularly, and 7900 to 9000 MPas.
About ductility, daiamid composition can show Notch angle (the otch slope angle using A type radius and 45 degree, notch angle) and under breach the depth of material of 8 millimeters, the hammer energy of 2.75 joules, 10 millimeters are multiplied by 4 millimeters of excellent cross-sectional dimension, and each composition ten samples, according at least 8.3 KJ (kilojoule)/rice that ISO 180:2000 determines at 23 DEG C 2notched Chalpy impact intensity.In some embodiments, notched Chalpy impact intensity is 8.3 to 10 KJ (kilojoule)/rice 2, particularly, 8.5 to 10 KJ (kilojoule)/rice 2.
(heat-resisting about heat resistanceheat resistant, heat resistance) performance, daiamid composition can show using method B120, under the penetration degree (needle penetration) of 1 millimeter of reading, the pre-loading time of 5 minutes, with each composition three samples, determine according to ISO 306:2004, the vicat softening temperature (Vicat softening temperature) of at least 200 DEG C.In some embodiments, vicat softening temperature is 200 to 250 DEG C, particularly, and 240 to 250 DEG C.
In some embodiments, daiamid composition shows UL94 grade, the melt viscosity of 100 to 160 pascals-second, the modulus in flexure of 7900 to 9000 MPas, 8.5 to the 10 KJ (kilojoule)/rice of V-0 2notched Chalpy impact intensity, and the vicat softening temperature of 240 to 250 DEG C.
A kind of embodiment is the method forming daiamid composition, the method comprises: based on the weight of daiamid composition, melt blending comprises the component of the following to form daiamid composition: poly-(phenylene ether) masterbatch of 5 to 30 weight percentage, first polymeric amide of 35 to 70 weight percentage, the glass fibre of 15 to 40 weight percentage, and the fire retardant comprising metal dialkyl phosphinates of 10 to 20 weight percentage; Wherein, based on the weight of poly-(phenylene ether) masterbatch, poly-(phenylene ether) masterbatch is the product that melt blending comprises the component of the following: poly-(phenylene ether) of 35 to 97 weight percentage, and the second polymeric amide of 3 to 65 weight percentage.
Use melt blending to form poly-(phenylene ether) masterbatch and daiamid composition.Use common device (as ribbon blending machine (ribbon blender), Henschel mixer (Henschel mixer), banbury mixers (Banbury mixer), drum tumbler (drum tumbler), single screw extrusion machine, twin screw extruder, multiple screw extruder, altogether kneader (co-kneader), etc.) that melt blending (being also called melt kneading) can be implemented.Such as, at 230 to 310 DEG C, particularly, at the temperature of 240 to 300 DEG C, (phenylene ether), the second polymeric amide can be gathered by melt blending in twin screw extruder, and any optional component implements the formation of poly-(phenylene ether) masterbatch.Such as, at 230 to 290 DEG C, particularly, the formation of daiamid composition can be implemented at the temperature of 250 to 270 DEG C by melt blending poly-(phenylene ether) masterbatch, the first polymeric amide, glass fibre and fire retardant.
Poly-(phenylene ether) masterbatch comprises poly-(phenylene ether).Poly-(phenylene ether) comprises those that comprise the repeated structural unit with following formula
Wherein, Z 1each appearance be all independently halogen, unsubstituted or replace C 1-C 12alkyl, condition is described hydrocarbyl group is not tertiary hydrocarbon base, C 1-C 12sulfenyl, C 1-C 12-oxyl, or C 2-C 12halogen-oxyl, wherein at least two carbon atoms separate halogen and Sauerstoffatom; And Z 2each appearance be hydrogen all independently, halogen, unsubstituted or replace C 1-C 12alkyl, condition is described hydrocarbyl group is not tertiary hydrocarbon base, C 1-C 12sulfenyl, C 1-C 12-oxyl, or C 2-C 12halogen-oxyl, wherein at least two carbon atoms separate halogen and Sauerstoffatom.As used in this article, no matter term " alkyl ", be used alone, or use as the prefix of other term, suffix or fragment, refers to the residue only comprising carbon and hydrogen.Residue can be aliphatics or aromatic series, straight chain, ring-type, two rings, branch, saturated or undersaturated.It can also comprise aliphatics, aromatic series, straight chain, ring-type, two rings, branch, the combination of saturated or unsaturated hydrocarbon moiety.But, when hydrocarbyl residue being described as replace, it can be included in alternatively more than the carbon of substituting group residue and hydrogen member or on heteroatoms.Therefore, when specifically describing as replacing, hydrocarbyl residue can also comprise one or more carbonyl groups, amino group, oh group, or analogue, or it can comprise heteroatoms in the main chain of hydrocarbyl residue.As an embodiment, Z 1it can be the di-n-butyl aminomethyl group formed by 3, the 5-dimethyl-Isosorbide-5-Nitrae-phenyl of end and two-n-Butyl Amine 99 component reaction of oxidative polymerization catalyst.
Poly-(phenylene ether) can comprise the molecule had containing aminoalkyl group end group (being typically positioned at the position at oh group ortho position).Also ever-present is tetramethyl biphenyl quinone (TMDQ) end group, typically obtains from the reaction mixture containing 2,6-xylenol that wherein there is tetramethyl biphenyl quinone by product.Poly-(phenylene ether) can be the form of homopolymer, multipolymer, graft copolymer, ionic polymer or segmented copolymer and their combination.
In some embodiments, poly-(phenylene ether) comprises poly-(phenylene ether)-polysiloxane block copolymers.As used in this article, term " poly-(phenylene ether)-polysiloxane block copolymers " refers to the block polymer comprising poly-(phenylene ether) block of at least one and at least one polysiloxane block.
In some embodiments, poly-(phenylene ether)-polysiloxane block copolymers is prepared by oxidation copolymerization method.In this approach, poly-(phenylene ether)-polysiloxane block copolymers is a kind of product of method, and the method comprises the monomer mixture that oxidation copolymerization comprises the polysiloxane of unitary phenol and hydroxyaryl end-blocking.In some embodiments, based on the gross weight of the polysiloxane of unitary phenol and hydroxyaryl end-blocking, monomer mixture comprises the unitary phenol of 70 to 99 weight parts, and the polysiloxane of the hydroxyaryl end-blocking of 1 to 30 weight part.The polysiloxane of hydroxyaryl end-blocking can comprise multiple repeating unit with following structure
Wherein, R 8each appearance be hydrogen, C all independently 1-C 12alkyl or C 1-C 12brine alkyl; With two terminal units with following structure
Wherein, Y is hydrogen, C 1-C 12alkyl, C 1-C 12-oxyl, or halogen, and wherein R 9each appearance be hydrogen, C independently 1-C 12alkyl or C 1-C 12brine alkyl.In a kind of very concrete embodiment, R 8and R 9occur it being methyl at every turn, and Y is methoxyl group.
In some embodiments, unitary phenol comprises 2,6-xylenol, and the polysiloxane of hydroxyaryl end-blocking has following structure
Wherein, n is on average 5 to 100, particularly, and 30 to 60.
Oxidation copolymerization method produces poly-(the phenylene ether)-polysiloxane block copolymers as desirable product and poly-(phenylene ether) as by product (not having the polysiloxane block combined).Poly-(phenylene ether) is separated from poly-(phenylene ether)-polysiloxane block copolymers is unnecessary.Therefore poly-(phenylene ether)-polysiloxane block copolymers can as " reaction product " comprising poly-(phenylene ether) and poly-(phenylene ether)-polysiloxane block copolymers.Some separating step, Tathagata, from isopropanol precipitating, can ensure the polysiloxane starting material of the hydroxyaryl end-blocking of the essentially no remnants of reaction product.In other words, these lock out operation ensure that the polysiloxane level of reaction product is all the form of poly-(phenylene ether)-polysiloxane block copolymers substantially.At the U.S. Patent number 8 of the people such as Carrillo, 017,697 and the people such as Carrillo in the U.S. Patent Application Serial 13/169,137 submitted on June 27th, 2011, describe method detailed for the formation of poly-(phenylene ether)-polysiloxane block copolymers.
In some embodiments, poly-(phenylene ether) to have in chloroform at 25 DEG C by the intrinsic viscosity of 0.25 to 1 deciliter every gram that Ubbelohde viscometer (Ubbelohde viscometer) is measured.Within this scope, poly-(phenylene ether) intrinsic viscosity can be 0.3 to 0.65 deciliter every gram, particularly, and 0.35 to 0.5 deciliter every gram, more specifically, 0.4 to 0.5 deciliter every gram.
In some embodiments, poly-(phenylene ether) comprises homopolymer or the multipolymer of monomer, and this monomer is selected from by 2,6-xylenol, 2,3,6-TMP, and the group of their combination composition.In some embodiments, poly-(phenylene ether) comprises poly-(phenylene ether)-polysiloxane block copolymers.In these embodiments, poly-(phenylene ether)-polysiloxane block copolymers is passable, such as, for daiamid composition provides 0.05 to 2 weight percentage, particularly, 0.1 to 1 weight percentage, more specifically, the siloxane groups of 0.2 to 0.8 weight percentage.
Based on the weight of poly-(phenylene ether) masterbatch, the amount of poly-(phenylene ether) is 35 to 97 weight percentage.Within this scope, the amount of poly-(phenylene ether) can be 50 to 97 weight percentage, particularly, and 75 to 96.5 weight percentage, more specifically, 85 to 95 weight percentage.
Based on the weight of daiamid composition, the amount of poly-(phenylene ether) can be 1.75 to 29.1 weight percentage.Within this scope, the amount of poly-(phenylene ether) can be 3 to 20 weight percentage, particularly, and 5 to 15 weight percentage, more specifically, 3 to 13 weight percentage.In some embodiments, daiamid composition comprises and is less than or equal to 19 weight percentage, particularly, is less than or equal to 17 weight percentage, more specifically, is less than or equal to poly-(phenylene ether) of 15 weight percentage.In some embodiments, daiamid composition comprises and is less than or equal to 13 weight percentage, particularly, is less than or equal to poly-(phenylene ether) of 11 weight percentage.
It can be the first identical or different polymeric amide and the second polymeric amide that daiamid composition comprises.Polymeric amide (being also called nylon) exists for feature with multiple acid amides (-C (O) NH-) group, and at the U.S. Patent number 4,970 of Gallucci, is described in 272.The polymeric amide being applicable to using as the first polymeric amide or the second polymeric amide in the methods of the invention comprises polymeric amide-6, polymeric amide-6, 6, polymeric amide-4, 6, polyamide-11, polymeric amide-12, polymeric amide-6, 10, polymeric amide-6, 12, polymeric amide-6/6, 6, polymeric amide-6/6, 12, polymeric amide-MXD, 6, polymeric amide-6, T, polymeric amide-6, I, polymeric amide-6/6, T, polymeric amide-6/6, I, polymeric amide-6, 6/6, T, polymeric amide-6, 6/6, I, polymeric amide-6/6, T/6, I, polymeric amide-6, 6/6, T/6, I, polymeric amide-6/12/6, T, polymeric amide-6, 6/12/6, T, polymeric amide-6/12/6, I, polymeric amide-6, 6/12/6, I, with their combination.In some embodiments, the first polymeric amide and/or the second polymeric amide comprise polymeric amide-6.In some embodiments, the first polymeric amide and/or the second polymeric amide comprise polymeric amide-6,6.In some embodiments, the first polymeric amide comprises polymeric amide-6,6, and the second polymeric amide comprises polymeric amide-6.In some embodiments, the first polymeric amide and the second polymeric amide comprise polymeric amide-6,6.
Polymeric amide can be prepared by many known methods, and polymeric amide is purchased from various source.
Based on the weight of poly-(phenylene ether) masterbatch, the amount of the second polymeric amide is 3 to 65 weight percentage.Within this scope, the amount of the second polymeric amide can be 3 to 40 weight percentage, particularly, and 3 to 20 weight percentage, more specifically, 3 to 10 weight percentage.
Based on the weight of daiamid composition, the amount of the second polymeric amide can be 0.15 to 19.5 weight percentage.Within this scope, the amount of the second polymeric amide can be 0.2 to 5 weight percentage, particularly, and 0.2 to 2 weight percentage, more specifically, 0.2 to 1 weight percentage.
Based on the weight of daiamid composition, the amount of the first polymeric amide is 35 to 70 weight percentage.Within this scope, the amount of the first polymeric amide can be 40 to 65 weight percentage, particularly, and 45 to 55 weight percentage.
Based on the weight of daiamid composition, the amount (that is, the summation of the amount of the first polymeric amide and the amount of the second polymeric amide) of total polymeric amide can be 35.15 to 73.25 weight percentage.Within this scope, the amount of total polymeric amide can be 40 to 60 weight percentage, particularly, and 45 to 55 weight percentage.In some embodiments, daiamid composition comprises and is less than or equal to 52 weight percentage, particularly, is less than or equal to the first polymeric amide and second polymeric amide of the combination of 50 weight percentage.
Poly-(phenylene ether) masterbatch can comprise the expanding material of poly-(phenylene ether) and the second polymeric amide alternatively further.As used in this article, term " expanding material " refers to and poly-(phenylene ether), the second polymeric amide, or both interactional polyfunctional compounds.This interaction can be (such as, the affecting the surface characteristic of disperse phase) of chemical (such as, grafting) and/or physics.
The example of the expanding material that can adopt comprises liquid diene polymer, epoxy resin compound, the polyolefin-wax of oxidation, quinone, organic silane compound, polyfunctional compound, and their combination.Expanding material further at the U.S. Patent number 5,132,365 of Gallucci, and describes in the people's such as Koevoets 6,593,411 and 7,226,963.
In some embodiments, expanding material comprises polyfunctional compound.Three types can be generally as the polyfunctional compound of expanding material.The polyfunctional compound of the first kind has (a) carbon-to-carbon double bond or carbon-to-carbon triple bond in the molecule, (b) at least one carboxylic acid, acid anhydrides, acid amides, ester, imide, amino, epoxide, ortho ester (orthoester), or oh group.The example of polyfunctional compound like this comprises toxilic acid; Maleic anhydride; Fumaric acid (fumaric acid, fumaricacid); Glycidyl acrylate, methylene-succinic acid; Equisetic acid; Maleimide; Regulox; From the reaction product that diamines and maleic anhydride, toxilic acid, fumaric acid etc. obtain; Dichloromaleic anhydride; Maleic acid; Undersaturated dicarboxylic acid (such as, vinylformic acid, butenoic acid, methacrylic acid, ethylacrylic acid, pentenoic acid, decylenic acid, undecylenic acid, dodecenoic acid acid, linolic acid etc.); The ester of above-mentioned unsaturated carboxylic acid, acid amides or acid anhydrides; Unsaturated alcohol (such as, alkanol, crotyl alcohol, methyl ethylene methyl alcohol, 4-amylene-1-ol, Isosorbide-5-Nitrae-hexadiene-3-alcohol, 3-butene-1, own-2, the 5-glycol of 4-glycol, 2,5-dimethyl-3-and formula C nh 2n-5oH, C nh 2n-7oH and C nh 2n-9the alcohol of OH, wherein, n is the positive integer of 10 to 30); With-NH 2the unsaturated amine that-OH the group that group replaces unsaturated alcohol above obtains; The diene polymer of functionalization and multipolymer; Comprise above-mentioned in one or more combination.In some embodiments, expanding material comprises maleic anhydride and/or fumaric acid.
The multifunctional expanding material of Second Type has the group that (a) is represented by formula (OR); wherein R is hydrogen or alkyl, aryl, acyl group or carbonyldioxy group; b () each at least two groups in them can be identical or different; be selected from carboxylic acid, sour halogenide, acid anhydrides, sour halide anhydride, ester, ortho ester, acid amides, imido grpup, amino, and their various salt.This group expanding material typical is the aliphaticpolycarboxylic acid, ester and the acid amides that are expressed from the next:
(R IO) mR’(COOR II) n(CONR IIIR IV) s
Wherein, R' is straight or branched, has 2 to 20, or, more specifically, the saturated aliphatic hydrocarbon of 2 to 10 carbon atoms; R ibe hydrogen or have 1 to 10, or, more specifically, 1 to 6, or, even more specifically, the alkyl of 1 to 4 carbon atom, aryl, acyl group or carbonylic dioxo group; Each R iIbe hydrogen independently or have 1 to 20, or, more specifically, the alkyl or aryl of 1 to 10 carbon atom; Each R iIIand R iVbe hydrogen independently or have 1 to 10, or, more specifically, 1 to 6, or, even more specifically, the alkyl or aryl of 1 to 4 carbon atom; M equal 1 and (n+s) be more than or equal to 2, or, more specifically, equal 2 or 3, and n and s is more than or equal to zero separately, and wherein (OR i) to be equivalent to carbonyl be α or β, and at least two carbonyls are by 2 to 6 carbon atoms separately.Obviously, when corresponding substituting group have be less than 6 carbon atoms time, R i, R iI, R iII, and R iVit cannot be aryl.
The poly carboxylic acid be applicable to comprises, and such as, Citric Acid (citric acid, citric acid), oxysuccinic acid, and agaric acid (n-hexadecylcitric acid, agaricic acid), comprise their various commercially forms, as such as, and anhydrous and moisture acid; With comprise above-mentioned in one or more combination.In some embodiments, expanding material comprises Citric Acid.Illustrating of ester useful in this article comprises, such as, and acetyl citrate, single stearyl and/or distearyl citrate, etc.The acid amides be applicable to useful in this article comprises, such as, and N, N'-diethyl Citric Acid acid amides; N-phenyl Citric Acid acid amides; N-dodecyl Citric Acid acid amides; N, N'-docosyl Citric Acid acid amides; N-dodecyl malic acid.Derivative comprises their salt, comprises and the salt of amine and basic metal and alkaline metal salt.The example of the salt be applicable to comprises calcium malate, citrate of lime, potassium malate, and Potassium Citrate.
The polyfunctional expanding material of the 3rd type has (a) sour halide group and (b) at least one carboxylic acid, acid anhydrides, ester, epoxide, ortho ester or amide group, optimization acid or anhydride group in the molecule.In this group, the example of expanding material comprises Trimellitic Anhydride Chloride, chloroformyl succinic anhydride, chloro formyl succinic acid, chloroformyl Pyroglutaric acid, chloroformyl pentanedioic acid, chloroethanoyl succinic anhydride, chloroacetylsuccinic acid, trimellitic anhydride acid chloride and chloracetyl pentanedioic acid.In some embodiments, expanding material comprises Trimellitic Anhydride Chloride.
Above-mentioned expanding material can be added directly to other component of poly-(phenylene ether) masterbatch, or with poly-(phenylene ether) pre-reaction.When solubilizing agent at least partially and poly-(phenylene ether) pre-reaction of all or part, find with many before expanding material, the particularly improvement of polyfunctional Compound Phase capacitive.Should believe, these pre-reactions can cause expanding material and poly-(phenylene ether) to react and subsequently by its functionalization.Such as, poly-(phenylene ether) can with Citric Acid or maleic anhydride pre-reaction to be formed poly-(phenylene ether) of acid-functionalization, compared with poly-(phenylene ether) of non-functionalization, it has the consistency improved with the first and second polymeric amide.
When adopting expanding material in the preparation at compatible polymeric amide-poly-(phenylene ether) blend, the amount of use will depend on that the concrete expanding material of selection and its add concrete poly-(phenylene ether) and the second polymeric amide wherein.In some embodiments, based on the weight of poly-(phenylene ether) masterbatch, the amount of expanding material is 0.2 to 5 weight percentage, particularly, and 0.5 to 4 weight percentage, more specifically, 1 to 3 weight percentage.
Representing as in working Examples below, when exceedingly not damaging the characteristic of the daiamid composition obtained, poly-(phenylene ether) masterbatch can be prepared when there is no expanding material.
Poly-(phenylene ether) masterbatch can be included in one or more additives known in thermoplastics art alternatively further.Such as, poly-(phenylene ether) masterbatch can comprise additive alternatively further, this additive is selected from stablizer, lubricant, processing aid, anti-dripping agent, nucleator, UV barrier agent, dyestuff, pigment, antioxidant, static inhibitor, metal passivator, release agent, etc., and their combination.When it is present, based on the weight of poly-(phenylene ether) masterbatch, usually to be less than or equal to 5 weight percentage, particularly, be less than or equal to 2 weight percentage, more specifically, be less than or equal to the total amount of 1 weight percentage, use such additive.
Based on the weight of daiamid composition, use poly-(phenylene ether) masterbatch with the amount of 5 to 30 weight percentage.Within this scope, the amount of poly-(phenylene ether) masterbatch can be 5 to 25 weight percentage, particularly, and 5 to 15 weight percentage.Except poly-(phenylene ether) masterbatch and the first polymeric amide, daiamid composition comprises glass fibre.The glass fibre be applicable to comprises based on E, A, C, ECR, R, S, D, and NE glass, and those of quartz.In some embodiments, glass fibre has 2 to 30 microns, particularly, and 5 to 25 microns, more specifically, the diameter of 8 to 15 microns.In some embodiments, before mixing (compounding), the length of glass fibre is 2 to 7 millimeters, particularly, and 3 to 5 millimeters.Glass fibre can comprise so-called adhesion promoter alternatively to improve it and the consistency of gathering (phenylene ether) and polystyrene.Adhesion promoter comprises chromium complexes, silane, titanate (ester), zircoaluminate (ester), propylene maleic anhydride, reactive fibre element ester etc.The glass fibre be applicable to such as, is purchased from supplier's (comprise, OwensCorning, Nippon Electric Glass, PPG, and Johns Manville).
Based on the weight of daiamid composition, daiamid composition comprises the glass fibre of the amount of 15 to 40 weight percentage.Within this scope, the amount of glass fibre can be 18 to 35 weight percentage, particularly, and 20 to 30 weight percentage.
Except poly-(phenylene ether) masterbatch, the first polymeric amide and glass fibre, daiamid composition comprises fire retardant.Fire retardant comprises metal dialkyl phosphinates.As used in this article, term " metal dialkyl phosphinates " refers to a kind of salt, and it comprises at least one metallic cation and at least one dialkyl phosphinic acid negatively charged ion.In some embodiments, metal dialkyl phosphinates has with following formula
Wherein, R aand R bc independently of one another 1-C 6alkyl; M is calcium, magnesium, aluminium, or zinc; And d is 2 or 3.R aand R bexample comprise methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl, and phenyl.In some embodiments, R aand R bbe ethyl, M is aluminium, and d is 3 (that is, metal dialkyl phosphinates is three (diethyl phospho acid) aluminium).
In some embodiments, metal dialkyl phosphinates is the form of particulate.Metal dialkyl phosphinates particulate can have the median particle diameter (D50) being less than or equal to 40 microns, or, more specifically, be less than or equal to the D50 of 30 microns, or, even more specifically, be less than or equal to the D50 of 25 microns.
Based on the weight of daiamid composition, the amount of fire retardant is 10 to 20 weight percentage.Within this scope, the amount of fire retardant can be 12 to 18 weight percentage, particularly, and 13 to 17 weight percentage.Based on the weight of daiamid composition, the amount of metal dialkyl phosphinates can be 5 to 20 weight percentage.Within this scope, the amount of metal dialkyl phosphinates can be 6 to 15 weight percentage, particularly, and 7 to 13 weight percentage.When the amount of metal dialkyl phosphinates is less than 10 weight percentage, it is combined with other fire retardant, is at least 10 weight percentage to make the amount of total fire retardant.
In some embodiments, fire retardant comprises melamine polyphosphate further.In some embodiments, fire retardant comprises zinc borate further.In some embodiments, fire retardant comprises melamine polyphosphate and zinc borate further.In some embodiments, based on the gross weight of fire retardant, fire retardant comprises 50 to 76 weight percentage, particularly, and the metal dialkyl phosphinates of 55 to 70 weight percentage; 22 to 49 weight percentage, particularly, the melamine polyphosphate of 25 to 40 weight percentage, and 2 to 8 weight percentage, particularly, the zinc borate of 3 to 7 weight percentage.In some embodiments, based on the weight of daiamid composition, daiamid composition comprises the metal dialkyl phosphinates of 6 to 13 weight percentage and comprises the melamine polyphosphate of 3 to 7 weight percentage further, and the zinc borate of 0.2 to 2 weight percentage.
Daiamid composition can comprise the expanding material of poly-(phenylene ether) and the first polymeric amide alternatively further.This expanding material can be identical or different with any expanding material used in poly-(phenylene ether) master batch processing.Under the background of poly-(phenylene ether) masterbatch, above-described expanding material is suitable for poly-(phenylene ether) masterbatch of increase-volume and the first polymeric amide.In some embodiments, the expanding material used in the melt blending of the first polymeric amide with poly-(phenylene ether) masterbatch comprises Citric Acid, fumaric acid, toxilic acid, maleic anhydride, or the combination of above-mentioned at least two kinds.When it is present, based on the weight of daiamid composition, can with 0.1 to 5 weight percentage, particularly, the amount of 0.2 to 3 weight percentage is used in the expanding material used in the melt blending of the first polymeric amide and poly-(phenylene ether) masterbatch.In some embodiments, except comprise at poly-(phenylene ether) masterbatch those, daiamid composition does not comprise any expanding material.In some embodiments, daiamid composition does not comprise any expanding material.
Except any additive be included in poly-(phenylene ether) masterbatch, daiamid composition can comprise one or more additives alternatively further.Such as, daiamid composition can comprise additive alternatively further, this additive is selected from stablizer, releasing agent, lubricant, processing aid, anti-dripping agent, nucleator, UV barrier agent, dyestuff, pigment, antioxidant, static inhibitor, mineral oil, metal passivator, release agent, etc., and their combination.When it is present, based on the gross weight of daiamid composition, usually to be less than or equal to 5 weight percentage, particularly, be less than or equal to 2 weight percentage, more specifically, the total amount being less than or equal to 1 weight percentage uses such additive.Aluminum stearate is particularly suitable lubricant.
In some embodiments, daiamid composition does not comprise conductive filler material.Such as, for many electrically with the application of electronics, it is desirable that daiamid composition shows minimum electroconductibility.
In some embodiments, daiamid composition does not comprise impact modifier.Apply for many products, when not using impact modifier, the ductility of daiamid composition is enough.
Formed in the very concrete method of daiamid composition, the method comprises: based on the weight of daiamid composition, melt blending comprises the component of the following to form daiamid composition: poly-(phenylene ether) masterbatch of 5 to 14 weight percentage, 45 to 55 weight percentage comprise polymeric amide-6, first polymeric amide of 6, the glass fibre of 20 to 30 weight percentage, and the fire retardant comprising metal dialkyl phosphinates, melamine polyphosphate and zinc borate of 12 to 18 weight percentage; Wherein, based on the weight of poly-(phenylene ether) masterbatch, poly-(phenylene ether) masterbatch is the product that melt blending comprises the component of the following: the homopolymer comprising monomer of 75 to 96.5 weight percentage or poly-(phenylene ether) of multipolymer, this monomer is selected from by 2,6-xylenol, 2,3,6-pseudocuminol, and the group of their combination composition; Second polymeric amide comprising polymeric amide-6,6 of 3 to 24.5 weight percentage; With poly-(phenylene ether) of 0.5 to 4 weight percentage and the expanding material of the second polymeric amide; Wherein, based on the gross weight of composition, daiamid composition comprises poly-(phenylene ether) that be less than or equal to 13 weight percentage; And wherein, daiamid composition does not comprise conductive filler material and impact modifier.In some embodiments, poly-(phenylene ether) comprises poly-(phenylene ether)-polysiloxane block copolymers further.
The present invention comprises the daiamid composition prepared according to all changes of above-described method.
Other embodiment is daiamid composition, comprises the product of melt blending the following: the polymeric amide of 40 to 60 weight percentage; Poly-(phenylene ether) of 3 to 13 weight percentage; 12 to 18 weight percentage comprise metal dialkyl phosphinates, melamine polyphosphate, and the fire retardant of zinc borate; The polymeric amide of 0.1 to 2 weight percentage and the expanding material of poly-(phenylene ether); With the glass fibre of 20 to 40 weight percentage; Wherein, all weight percentage are the gross weights based on daiamid composition.Such composition can be formed by above-described method.Under the background of the method, polymeric amide and poly-(phenylene ether) can be selected from any above-described those.
In the very concrete embodiment of daiamid composition, polymeric amide comprises polymeric amide-6,6; Daiamid composition comprises the polymeric amide of 45 to 55 weight percentage; Poly-(phenylene ether) comprises homopolymer or the multipolymer of monomer, and this monomer is selected from by 2,6-xylenol, 2,3,6-TMP, and the group of their combination composition; Daiamid composition comprises poly-(phenylene ether) of 6 to 12 weight percentage; Fire retardant comprises the metal dialkyl phosphinates of 6 to 13 weight percentage, the melamine polyphosphate of 3 to 7 weight percentage, and the zinc borate of 0.2 to 2 weight percentage; And composition comprises the glass fibre of 20 to 30 weight percentage.In some embodiments, poly-(phenylene ether) comprises poly-(phenylene ether)-polysiloxane block copolymers further.
Other embodiment is included in the goods of any daiamid composition described herein.Daiamid composition is suitable for forming Electrical and Electronic element, especially, and isolating switch (comprising miniature circuit breaker); Remaining circuit assembly; Switch; Socket; Plug for industrial use; Electrical fitting (comprise for automobile, telecommunication, data corresponding, computer, and the junctor of electronic installation industry); For the switching arrangement of automobile, computer, telecommunication and mobile telephone industry; For heating, ventilating and the parts of cooling system; Mechanical part; For the parts of human consumer and Industrial products.The method be applicable to forming such goods comprises individual layer and multi-layered board is extruded, injection molding, blowing, film are extruded, section bar extrusion, pultrusion, compression molding, thermoforming, pressure forming, hydroforming, vacuum forming, etc.The combination of above-mentioned product and making method can be used.
In the very concrete embodiment of goods, polymeric amide comprises polymeric amide-6,6; Daiamid composition comprises the polymeric amide of 45 to 55 weight percentage; Poly-(phenylene ether) comprises homopolymer or the multipolymer of monomer, and this monomer is selected from by 2,6-xylenol, 2,3,6-TMP, and the group of their combination composition; Daiamid composition comprises poly-(phenylene ether) of 6 to 12 weight percentage; Fire retardant comprises the metal dialkyl phosphinates of 6 to 13 weight percentage, the melamine polyphosphate of 3 to 7 weight percentage, and the zinc borate of 0.2 to 2 weight percentage; And composition comprises the glass fibre of 20 to 30 weight percentage.In some embodiments, poly-(phenylene ether) comprises poly-(phenylene ether)-polysiloxane block copolymers further.
The present invention comprises poly-(phenylene ether) masterbatch.Therefore, a kind of embodiment is the weight that poly-(phenylene ether) masterbatch comprises based on poly-(phenylene ether) masterbatch, and melt blending comprises the product of the component of the following: poly-(phenylene ether) of 92 to 97 weight percentage; The polymeric amide of 3 to 4.8 weight percentage; And alternatively, poly-(phenylene ether) of 0.1 to 5 weight percentage and the expanding material of polymeric amide.In some embodiments, poly-(phenylene ether) masterbatch comprises the expanding material of 0.5 to 3 weight percentage.Except the amount of the component of specifying in this paragraph, all composition changes of above-described poly-(phenylene ether) masterbatch are applicable to poly-(phenylene ether) masterbatch of this paragraph.Such as, the polymeric amide of masterbatch of the present invention is equivalent to above-described second polymeric amide.In some embodiments, melt blending component comprises the additive of 0.2 to 0.5 weight percentage further, and this additive is selected from the group be made up of antioxidant, stablizer and their combination.In some embodiments, poly-(phenylene ether) masterbatch is made up of following: poly-(phenylene ether), polymeric amide, expanding material alternatively, the additive of 0.2 to 0.5 weight percentage alternatively, this additive is selected from the group be made up of antioxidant, stablizer and their combination.
In the very concrete embodiment of poly-(phenylene ether) masterbatch, poly-(phenylene ether) comprises homopolymer or the multipolymer of monomer, and this monomer is selected from by 2,6-xylenol, 2,3,6-pseudocuminol, and the group of their combination composition; The component of melt blending comprises poly-(phenylene ether) of 92 to 95 weight percentage; Polymeric amide comprises polymeric amide-6,6; The component of melt blending comprises the polymeric amide of 4 to 4.8 weight percentage; Expanding material is selected from the group be made up of Citric Acid, toxilic acid, maleic anhydride and their combination; And the component of melt blending comprises the expanding material of 0.5 to 3 weight percentage.In this embodiment, poly-(phenylene ether) masterbatch can comprise the additive of 0.2 to 0.5 weight percentage alternatively further, and this additive is selected from the group be made up of antioxidant, stablizer and their combination.
The present invention includes and use poly-(phenylene ether) masterbatch to reduce the metal dialkyl phosphinates content of retardant polyamide composition.Particularly, a kind of embodiment is the method for the metal dialkyl phosphinates content reducing retardant polyamide composition, comprise: based on the weight of daiamid composition, melt blending comprises the component of the following to form daiamid composition: poly-(phenylene ether) masterbatch of 5 to 30 weight percentage, first polymeric amide of 35 to 70 weight percentage, the glass fibre of 15 to 40 weight percentage, and the fire retardant comprising metal dialkyl phosphinates of 10 to 20 weight percentage; Wherein, based on the weight of poly-(phenylene ether) masterbatch, poly-(phenylene ether) masterbatch is the product that melt blending comprises the component of the following: poly-(phenylene ether) of 35 to 97 weight percentage, and the second polymeric amide of 3 to 65 weight percentage.Under the background of method forming daiamid composition, above-described all modification are also applicable to the method for the metal dialkyl phosphinates content reducing retardant polyamide composition.
The present invention at least comprises following embodiment.
Embodiment 1: the method forming daiamid composition, the method comprises: based on the weight of daiamid composition, melt blending comprises the component of the following to form daiamid composition: poly-(phenylene ether) masterbatch of 5 to 30 weight percentage, first polymeric amide of 35 to 70 weight percentage, the glass fibre of 15 to 40 weight percentage, and the fire retardant comprising metal dialkyl phosphinates of 10 to 20 weight percentage; Wherein, based on the weight of poly-(phenylene ether) masterbatch, poly-(phenylene ether) masterbatch is the product that melt blending comprises the component of the following: poly-(phenylene ether) of 35 to 97 weight percentage, and the second polymeric amide of 3 to 65 weight percentage.
Embodiment 2: the method in embodiment 1, wherein, first polymeric amide and the second polymeric amide are independently selected from by polymeric amide-6, polymeric amide-6, 6, polymeric amide-4, 6, polyamide-11, polymeric amide-12, polymeric amide-6, 10, polymeric amide-6, 12, polymeric amide-6/6, 6, polymeric amide-6/6, 12, polymeric amide-MXD, 6, polymeric amide-6, T, polymeric amide-6, I, polymeric amide-6/6, T, polymeric amide-6/6, I, polymeric amide-6, 6/6, T, polymeric amide-6, 6/6, I, polymeric amide-6/6, T/6, I, polymeric amide-6, 6/6, T/6, I, polymeric amide-6/12/6, T, polymeric amide-6, 6/12/6, T, polymeric amide-6/12/6, I, polymeric amide-6, 6/12/6, I, with the group of their combination composition.
Embodiment 3: the method in embodiment 1, wherein, the first polymeric amide and the second polymeric amide are independently selected from by polymeric amide-6, polymeric amide-6,6, and the group of their combination composition.
Embodiment 4: the method in embodiment 1, wherein, the first polymeric amide and the second polymeric amide comprise polymeric amide-6,6.
Embodiment 5: the method any one of embodiment 1-4, wherein, daiamid composition comprises the first polymeric amide and second polymeric amide of the combination being less than or equal to 52 weight percentage.
Embodiment 6: the composition any one of embodiment 1-5, wherein, poly-(phenylene ether) comprises homopolymer or the multipolymer of monomer, and this monomer is selected from by 2,6-xylenol, 2,3,6-TMP, and the group of their combination composition.
Embodiment 7: the method any one of embodiment 1-6, wherein, poly-(phenylene ether) comprises poly-(phenylene ether)-polysiloxane block copolymers.
Embodiment 8: the method any one of embodiment 1-7, wherein, based on the weight of daiamid composition, daiamid composition comprises poly-(phenylene ether) that be less than or equal to 19 weight percentage.
Embodiment 9: the method any one of embodiment 1-8, wherein, based on the weight of daiamid composition, daiamid composition comprises poly-(phenylene ether) that be less than or equal to 13 weight percentage.
Embodiment 10: the method any one of embodiment 1-9, wherein, fire retardant comprises melamine polyphosphate further.
Embodiment 11: the method any one of embodiment 1-10, wherein, fire retardant comprises zinc borate further.
Embodiment 12: the method any one of embodiment 1-11, wherein, based on the weight of daiamid composition, fire retardant comprises the metal dialkyl phosphinates of 6 to 13 weight percentage and comprises the melamine polyphosphate of 3 to 7 weight percentage further, and the zinc borate of 0.2 to 2 weight percentage.
Embodiment 13: the method any one of embodiment 1-12, wherein, based on the weight of poly-(phenylene ether) masterbatch, poly-(phenylene ether) masterbatch comprises poly-(phenylene ether) of 0.2 to 5 weight percentage and the expanding material of the second polymeric amide further.
Embodiment 14: the method any one of embodiment 1-13, wherein, daiamid composition does not comprise conductive filler material.
Embodiment 15: the method any one of embodiment 1-14, wherein, daiamid composition does not comprise impact modifier.
Embodiment 16: the method for embodiment 1, wherein, melt blending comprises the fire retardant of poly-(phenylene ether) masterbatch, the first polymeric amide of 45 to 55 weight percentage, the glass fibre of 20 to 30 weight percentage and 12 to 18 weight percentage of 5 to 14 weight percentage with the component forming daiamid composition; Wherein, fire retardant comprises melamine polyphosphate and zinc borate further; Wherein, melt blending comprises poly-(phenylene ether) of 75 to 96.5 weight percentage with the component forming poly-(phenylene ether) masterbatch, and the second polymeric amide of 3 to 24.5 weight percentage; And wherein, poly-(phenylene ether) comprises homopolymer or the multipolymer of monomer, and this monomer is selected from by 2,6-xylenol, 2,3,6-TMP, and the group of their combination composition; Wherein, the second polymeric amide comprises polymeric amide-6,6; Wherein, melt blending comprises poly-(phenylene ether) of 0.5 to 4 weight percentage and the expanding material of the second polymeric amide further with the component forming poly-(phenylene ether) masterbatch; Wherein, based on the gross weight of composition, daiamid composition comprises poly-(phenylene ether) that be less than or equal to 13 weight percentage; And wherein, daiamid composition does not comprise conductive filler material and impact modifier.
Embodiment 16a: the method forming daiamid composition, the method comprises: based on the weight of daiamid composition, melt blending comprises the component of the following to form daiamid composition: poly-(phenylene ether) masterbatch of 5 to 14 weight percentage, 45 to 55 weight percentage comprise polymeric amide-6, first polymeric amide of 6, the glass fibre of 20 to 30 weight percentage, with 12 to 18 weight percentage comprise metal dialkyl phosphinates, melamine polyphosphate, and the fire retardant of zinc borate; Wherein, based on the weight of poly-(phenylene ether) masterbatch, poly-(phenylene ether) masterbatch is the product that melt blending comprises the component of the following: the homopolymer comprising monomer of 75 to 96.5 weight percentage or poly-(phenylene ether) of multipolymer, this monomer is selected from by 2,6-xylenol, 2,3,6-pseudocuminol, and the group of their combination composition; Second polymeric amide comprising polymeric amide-6,6 of 3 to 24.5 weight percentage; With poly-(phenylene ether) of 0.5 to 4 weight percentage and the expanding material of the second polymeric amide; Wherein, based on the gross weight of composition, daiamid composition comprises poly-(phenylene ether) that be less than or equal to 13 weight percentage; And wherein, daiamid composition does not comprise conductive filler material and impact modifier.
Embodiment 17: the method for embodiment 16, wherein, poly-(phenylene ether) comprises poly-(phenylene ether)-polysiloxane block copolymers further.
Embodiment 18: daiamid composition prepared by the method any one of embodiment 1-17.
Embodiment 19: a kind of daiamid composition, comprises the product of melt blending the following: the polymeric amide of 40 to 60 weight percentage; Poly-(phenylene ether) of 3 to 13 weight percentage; 12 to 18 weight percentage comprise metal dialkyl phosphinates, melamine polyphosphate, and the fire retardant of zinc borate; The polymeric amide of 0.1 to 2 weight percentage and the expanding material of poly-(phenylene ether); With the glass fibre of 20 to 40 weight percentage; Wherein, all weight percentage are the gross weights based on daiamid composition.
Embodiment 20: the daiamid composition of embodiment 19, wherein, polymeric amide comprises polymeric amide-6,6; Wherein, daiamid composition comprises the polymeric amide of 45 to 55 weight percentage; Wherein, poly-(phenylene ether) comprises homopolymer or the multipolymer of monomer, and this monomer is selected from by 2,6-xylenol, 2,3,6-TMP, and the group of their combination composition; Wherein, daiamid composition comprises poly-(phenylene ether) of 6 to 12 weight percentage; Wherein, fire retardant comprises the metal dialkyl phosphinates of 6 to 13 weight percentage, the melamine polyphosphate of 3 to 7 weight percentage, and the zinc borate of 0.2 to 2 weight percentage; Wherein, composition comprises the glass fibre of 20 to 30 weight percentage.
Embodiment 21: the daiamid composition of embodiment 20, wherein, poly-(phenylene ether) comprises poly-(phenylene ether)-polysiloxane block copolymers further.
Embodiment 22: a kind of goods comprising the composition of the product comprising melt blending the following: the polymeric amide of 40 to 60 weight percentage; Poly-(phenylene ether) of 3 to 13 weight percentage; 12 to 18 weight percentage comprise metal dialkyl phosphinates, melamine polyphosphate, and the fire retardant of zinc borate; The polymeric amide of 0.1 to 2 weight percentage and the expanding material of poly-(phenylene ether); With the glass fibre of 20 to 40 weight percentage; Wherein, all weight percentage are the gross weights based on daiamid composition.
Embodiment 23: the method reducing the metal dialkyl phosphinates content of retardant polyamide composition, comprise: based on the weight of daiamid composition, melt blending comprises the component of the following to form daiamid composition: poly-(phenylene ether) masterbatch of 5 to 30 weight percentage, first polymeric amide of 35 to 70 weight percentage, the glass fibre of 15 to 40 weight percentage, and the fire retardant comprising metal dialkyl phosphinates of 10 to 20 weight percentage; Wherein, based on the weight of poly-(phenylene ether) masterbatch, poly-(phenylene ether) masterbatch is the product that melt blending comprises the component of the following: poly-(phenylene ether) of 35 to 97 weight percentage, and the second polymeric amide of 3 to 65 weight percentage.
Embodiment 24: based on the weight of poly-(phenylene ether) masterbatch, poly-(phenylene ether) masterbatch comprises the product that melt blending comprises the component of the following: poly-(phenylene ether) of 92 to 97 weight percentage; The polymeric amide of 3 to 4.8 weight percentage; And alternatively, poly-(phenylene ether) of 0.1 to 5 weight percentage and the expanding material of polymeric amide.
Embodiment 25: poly-(phenylene ether) masterbatch of embodiment 24, comprises the expanding material of 0.5 to 3 weight percentage.
Embodiment 26: poly-(phenylene ether) masterbatch of embodiment 24 or 25, wherein, the component of melt blending comprises the additive of 0.2 to 0.5 weight percentage further, and this additive is selected from the group formed by antioxidant, stablizer and their combination.
Embodiment 27: poly-(phenylene ether) masterbatch any one of embodiment 24-26, be made up of the following: poly-(phenylene ether), polymeric amide, expanding material alternatively, the additive of 0.2 to 0.5 weight percentage alternatively, this additive is selected from the group be made up of antioxidant, stablizer and their combination.
Embodiment 28: poly-(phenylene ether) masterbatch of embodiment 24, wherein, poly-(phenylene ether) comprises homopolymer or the multipolymer of monomer, this monomer is selected from by 2,6-xylenol, and 2,3,6-pseudocuminol, and the group of their combination composition; Wherein, the component of melt blending comprises poly-(phenylene ether) of 92 to 95 weight percentage; Wherein, polymeric amide comprises polymeric amide-6,6; Wherein, the component of melt blending comprises the polymeric amide of 4 to 4.8 weight percentage; Wherein, expanding material is selected from by Citric Acid, toxilic acid, maleic anhydride, and the group of their combination composition; Wherein, the component of melt blending comprises the expanding material of 0.5 to 3 weight percentage.
Embodiment 29: poly-(phenylene ether) masterbatch of embodiment 28, wherein, the component of melt blending comprises the additive of 0.2 to 0.5 weight percentage further, and this additive is selected from by antioxidant, stablizer, and the group of their combination composition.
Disclosed all scopes comprise end points in this article, and end points can independently combine mutually.Disclosed each scope is formed in disclosing of any point within scope of disclosure or subrange in this article.
The embodiment limited by following non-sets forth the present invention further.
Preparation embodiment 1-12
These embodiments illustrate the preparation of masterbatch.
Outline the component for the formation of masterbatch in Table 1, and the composition described in the examples below.
Table 1
Poly-(phenylene ether) masterbatch of ZSK twin screw extruder preparation of 28 millimeters of internal diameters is used under the treatment capacity of the melt temperature of 240-300 DEG C and 15 kgs/hr.PPE or PPE-Si of powder type and antioxidant and stablizer and Citric Acid dry blend, be in the dry blends introduced in the first feeder and obtain subsequently at the trunnion of forcing machine, and via the second feeder downstream charging PA66 or PA6.Summarize concentrate composition in table 2, wherein the amount of component represents with weight part.
Table 2
Table 2 (continuation).
Embodiment 1-8, comparing embodiment 1-5
These embodiments illustrate the composition with poly-(phenylene ether) master batch processing comprising polymeric amide-6,6.These embodiments to be presented at when reducing the flame retardant additives of concentration and when not utilizing unmanageable poly-(phenylene ether) powder, can by the fire-retardant polymeric amide concentration of preparation.
The ZSK twin screw extruder of the 28 millimeters of internal diameters operated under being used in the treatment capacity of the melt temperature of 250-270 DEG C and 15 kgs/hr prepares daiamid composition.In sack, manually shake makes masterbatch and other stablizer and Citric Acid be mixed together, and introduces the blend of the drying obtained at the trunnion place of forcing machine in the first feeder.Via the downstream second feeder charging PA66 of the first feeder to forcing machine, and introduce glass fibre via the 3rd, the downstream feeder of the second feeder.
Use the barrel temperature of 250-290 DEG C, and the molding temperature of 80-100 DEG C, injection molding is used for the test article of physical testing.
Use the temperature of 282 DEG C and multipoint iterations to carry out melt viscosity test according to ISO 11443:2005, wherein measure the melt viscosity under various shearing rate.In table 2,1,500 seconds -1the melt viscosity value with the unit of pascal-second is measured under shearing rate.
Use has 80 millimeters and is multiplied by the 1A types rod that 10 millimeters are multiplied by 4 mm sizes, the gauge length of 50 millimeters, the fixture of 115 millimeters is separated (grip separation), the test speed of 1 mm/min, with each composition 5 samples, at 23 DEG C, the tensile modulus values expressed in units of MPa is determined according to ISO 527-1:2012, and with the break-draw strain value that percentage ratio is expressed.
Use 80 millimeters to be multiplied by the excellent transversal dimensions that 10 millimeters are multiplied by 4 millimeters, the bearing stride of 64 millimeters and each composition three samples determine the modulus in flexure expressed in units of MPa and flexural strength according to ISO178:2010 at 23 DEG C.
Use A type radius and 45 degree Notch angle and under breach the degree of depth of 8 millimeters of materials, the hammer energy of 2.75 joules, 10 millimeters are multiplied by the excellent cross-sectional dimension of 4 millimeters and each composition ten samples, according to ISO 180:2000, determine with KJ (kilojoule)/rice at 23 DEG C and-30 DEG C 2for the notched Chalpy impact intensity level that unit expresses.
Using method B120, the penetration degree of 1 millimeter of reading, the pre-loading time of 5 minutes, and each composition three samples, according to ISO 306:2004 determine by degree Celsius in units of express vicat softening temperature value.
According to the laboratory bulletin 94 " the combustibility test of plastic material, UL 94 " of underwriter, 20mm Vertical Burning Flame is tested, and determines the flame retardant resistance of injection molding flame rod.Before test, the flame rod pre-treatment at least 48 hours of 0.8 mm of thickness will be had under 23 DEG C and 50% relative humidity.Test is modified to and uses a set of ten flame rods instead of common five.For each rod, apply flame and then remove to rod, and record the time (the first tail-off time (firstafterflame time), t1) required for excellent self-gravitation.Again apply flame subsequently and remove, and (second tail-off time (second afterflame time) time of recording required for excellent self-gravitation, t2) fluorescent lifetime (post-flame glowing time) (time of persistence (afterglow time), t3) and after flame.In order to realize V-0 grade, tail-off time t1 and t2 of at least nine in ten single samples is necessarily less than or equal to 10 seconds (grade record compositions in table 2, for said composition, one in ten single samples has the tail-off time being greater than 10 seconds); And all ten sample total tail-off times (t1 of all ten samples adds t2) are necessarily less than or equal to 100 seconds; And the second tail-off time of each single sample adds time of persistence (t2+t3) and is necessarily less than or equal to 30 seconds; And do not have sample to burn or to burn to holding clamp; And cotton indicator can not be burned particle or dropping light.In order to realize the grade of V-1, tail-off time t1 and t2 of each single sample is necessarily less than or equal to 30 seconds; And total tail-off time of all ten samples (t1 of all ten samples adds t2) is necessarily less than or equal to 500 seconds; And each single sample second tail-off time adds and is necessarily less than or equal to 60 seconds time of persistence (t2+t3); And do not have sample to burn or to burn to holding clamp; And cotton indicator can not be burned particle or dropping light.In order to realize the grade of V-2, tail-off time t1 and t2 of each single sample is necessarily less than or equal to 30 seconds; And total tail-off time of all ten samples (t1 of all ten samples adds t2) is necessarily less than or equal to 250 seconds; And the second tail-off time of each single sample adds time of persistence (t2+t3) and is necessarily less than or equal to 60 seconds; And do not have sample to burn or to burn to holding clamp; But the particle that cotton indicator can be burned or dropping are lighted.The composition not reaching V-2 standard is considered to failure.In table 3, " UL 94TFT (second) " is the summation of the t1 value of ten all samples.
Use the test sample with the thickness of 3.2 millimeters and the diameter of 10 centimetres, often kind of composition five samples, according to International Electrotechnical Commission (IEC) standard IEC-60112, the third edition these (1979) implements phase ratio creepage tracking index (CTI) value expressed in units of volt.Report value is the voltage having caused creepage trace after 50 ammonium chloride solutions have dropped on material surface.
Comparing embodiment 1 and 2, and embodiment 1-3 and 7 illustrates as powder (comparing embodiment 2) or the effect of poly-(phenylene ether) of adding with masterbatch (embodiment 1-3 and 7).The interpolation of poly-(phenylene ether) allows the amount of fire retardant to reduce about 29% (from 21 weight percentage to 15 weight percentage), maintains desirable V-0 or V-1 grade in UL 94 flammability test simultaneously.Embodiment 2 and 3 (it utilizes the masterbatch with expanding material Citric Acid and higher poly-(phenylene ether) content) shows V-0 grade.Relative to comparing embodiment 1 and 2, mechanical property is also kept significantly.And the difficult treatment relevant to poly-(phenylene ether) powder is avoided in the use of masterbatch in embodiment 1-3 is with 7.
Comparing embodiment 4 and embodiment 3 illustrate the effect comprising polymeric amide in poly-(phenylene ether) masterbatch.Relative to comparing embodiment 4 (not having polymeric amide in masterbatch), embodiment 3 (with polymeric amide in masterbatch) demonstrates excellent flame retardant resistance and fluidity of molten.
Comparing embodiment 1 and 3, and embodiment 4-6 and 8 describes as powder (comparing embodiment 3) or with the effect of poly-(phenylene ether)-polysiloxane block copolymers reaction product of masterbatch (embodiment 4-6 and 8).The interpolation of poly-(phenylene ether)-polysiloxane block copolymers reaction product allows the amount of fire retardant to reduce about 29% (from 21 weight percentage to 15 weight percentage), maintains desirable V-0 or V-1 grade in UL 94 flammability test simultaneously.Not relevant to expanding material or poly-(phenylene ether)-polysiloxane block copolymers reaction product content clearly trend, but embodiment 4,6, and 8 all show V-0 grade.Relative to comparing embodiment 1 and 3, mechanical property is also kept significantly.In embodiment 4-6 is with 8, the difficult treatment relevant to poly-(phenylene ether)-polysiloxane reaction product powder is avoided in the use of masterbatch.
Embodiment 1 and 4 illustrates, even when not using expanding material, can obtain benefit of the present invention.
Table 3
* one in ten samples has the tail-off time of being longer than 10 seconds
Table 3 (continuation)
* in ten samples, one has the tail-off time of being longer than 10 seconds
Table 3 (continuation).
* one in ten samples has the tail-off time of being longer than 10 seconds
Embodiment 11-18, comparing embodiment 4-5
These embodiments illustrate the composition with poly-(phenylene ether) master batch processing comprising polymeric amide-6.These embodiments demonstrate can prepare fire-retardant daiamid composition when not utilizing reluctant (phenylene ether) powder when reducing the flame retardant additives of concentration.
Service routine B (displacement-measure, automatic method), the probe temperature of 300 DEG C, 5 kilograms of loadings applied, the capillary diameter of 2.0995 millimeters, the capillary pipe length of 8.0 millimeters, the test sample of pellets, sample pretreatment 5.5 hours at 120 DEG C before testing, and often kind of composition once runs five readings, determines the melting volume-flow rate value expressed in units of cubic centimetre by every 10 minutes according to ISO 1133-2005.
Except sample not breach, for the notched izod value at 23 DEG C, measure with KJ (kilojoule)/rice 2unit express non-notch cantilever beam impact strength value.
UL 94 grade is determined under 0.8 and 1.5 mm of thickness.
Result display in table 4, with the masterbatch of polymeric amide-6 and poly-(phenylene ether) or poly-(phenylene ether)-polysiloxane block copolymers at polymeric amide-6,6 compositions (embodiment 11-14), with be effective in polymeric amide-6 composition (embodiment 15-18), produce UL 94 grade of V-0 or V-1 with the fire retardant of the amount reduced.V-0 or the V-1 grade of polymeric amide-6 composition of embodiment 15-18 is better than the V-2 grade of the corresponding comparing embodiment 4 and 5 using poly-(phenylene ether) powder and poly-(phenylene ether)-polysiloxane block copolymers powder respectively.V-0 grade under 0.8 mm of thickness is by embodiment 13 and 17 (having the masterbatch of comprising of 20 weight percentage poly-(phenylene ether)) and embodiment 18 (having the masterbatch of comprising of 20 weight percentage of poly-(phenylene ether)-polysiloxane block copolymers reaction product) display.Be similar to the mechanical property of the blend manufactured with powder by the mechanical property of the blend of masterbatch manufacture, but use masterbatch to avoid the difficulty relevant with poly-(phenylene ether) powder treatment.
Table 4
* one in ten samples has the tail-off time of being longer than 10 seconds
Table 4 (continuation)
* in ten samples, one has the tail-off time of being longer than 10 seconds.

Claims (23)

1. form a method for daiamid composition, described method comprises:
Based on the weight of described daiamid composition, melt blending comprises the component of the following, to form described daiamid composition:
Poly-(phenylene ether) masterbatch of 5 to 30 weight percentage,
First polymeric amide of 35 to 70 weight percentage,
The glass fibre of 15 to 40 weight percentage, and
The fire retardant comprising metal dialkyl phosphinates of 10 to 20 weight percentage;
Wherein, based on the weight of described poly-(phenylene ether) masterbatch, described poly-(phenylene ether) masterbatch is the product that melt blending comprises the component of the following:
Poly-(phenylene ether) of 35 to 97 weight percentage, and
Second polymeric amide of 3 to 65 weight percentage.
2. method according to claim 1, wherein, described first polymeric amide and described second polymeric amide are independently selected from by polymeric amide-6, polymeric amide-6, 6, polymeric amide-4, 6, polyamide-11, polymeric amide-12, polymeric amide-6, 10, polymeric amide-6, 12, polymeric amide-6/6, 6, polymeric amide-6/6, 12, polymeric amide MXD, 6, polymeric amide-6, T, polymeric amide-6, I, polymeric amide-6/6, T, polymeric amide-6/6, I, polymeric amide-6, 6/6, T, polymeric amide-6, 6/6, I, polymeric amide-6/6, T/6, I, polymeric amide-6, 6/6, T/6, I, polymeric amide-6/12/6, T, polymeric amide-6, 6/12/6, T, polymeric amide-6/12/6, I, polymeric amide-6, 6/12/6, I, with the group of their combination composition.
3. method according to claim 1, wherein, described first polymeric amide and described second polymeric amide are independently selected from by polymeric amide-6, polymeric amide-6,6, and the group of their combination composition.
4. method according to claim 1, wherein, described first polymeric amide and described second polymeric amide comprise polymeric amide-6,6.
5. the method according to any one of claim 1-4, wherein, described daiamid composition comprises described first polymeric amide of the combination being less than or equal to 52 weight percentage and described second polymeric amide.
6. the composition according to any one of claim 1-5, wherein, described poly-(phenylene ether) comprises homopolymer or the multipolymer of the monomer being selected from the group be made up of the following: 2,6-xylenol, 2,3,6-pseudocuminol, and their combination.
7. the method according to any one of claim 1-6, wherein, described poly-(phenylene ether) comprises poly-(phenylene ether)-polysiloxane block copolymers.
8. the method according to any one of claim 1-7, wherein, based on the weight of described daiamid composition, described daiamid composition comprises poly-(phenylene ether) that be less than or equal to 19 weight percentage.
9. the method according to any one of claim 1-8, wherein, based on the weight of described daiamid composition, described daiamid composition comprises poly-(phenylene ether) that be less than or equal to 13 weight percentage.
10. the method according to any one of claim 1-9, wherein, described fire retardant comprises melamine polyphosphate further.
11. methods according to any one of claim 1-10, wherein, described fire retardant comprises zinc borate further.
12. the method according to any one of claim 1-11, wherein, based on the weight of described daiamid composition, described fire retardant comprises the described metal dialkyl phosphinates of 6 to 13 weight percentage and comprises the melamine polyphosphate of 3 to 7 weight percentage further, and the zinc borate of 0.2 to 2 weight percentage.
13. the method according to any one of claim 1-12, wherein, based on the weight of described poly-(phenylene ether) masterbatch, described poly-(phenylene ether) masterbatch comprises described poly-(phenylene ether) of 0.2 to 5 weight percentage and the expanding material of described second polymeric amide further.
14. methods according to any one of claim 1-13, wherein, described daiamid composition does not comprise conductive filler material.
15. methods according to any one of claim 1-14, wherein, described daiamid composition does not comprise impact modifier.
16. methods according to claim 1,
Wherein, melt blending comprises with the described component forming described daiamid composition
Described poly-(phenylene ether) masterbatch of 5 to 14 weight percentage,
Described first polymeric amide of 45 to 55 weight percentage,
The described glass fibre of 20 to 30 weight percentage, and
The described fire retardant of 12 to 18 weight percentage;
Wherein, described fire retardant comprises melamine polyphosphate and zinc borate further;
Wherein, melt blending comprises with the described component forming described poly-(phenylene ether) masterbatch
Poly-(phenylene ether) of 75 to 96.5 weight percentage, and
Described second polymeric amide of 3 to 24.5 weight percentage;
Wherein, described poly-(phenylene ether) comprises homopolymer or the multipolymer of the monomer being selected from the group be made up of the following: 2,6-xylenol, 2,3,6-TMP, and their combination;
Wherein, described second polymeric amide comprises polymeric amide-6,6;
Wherein, melt blending comprises described poly-(phenylene ether) of 0.5 to 4 weight percentage and the expanding material of described second polymeric amide further with the described component forming described poly-(phenylene ether) masterbatch;
Wherein, based on the gross weight of described composition, described daiamid composition comprises poly-(phenylene ether) that be less than or equal to 13 weight percentage; And
Wherein, described daiamid composition does not comprise conductive filler material and impact modifier.
17. methods according to claim 16, wherein, described poly-(phenylene ether) comprises poly-(phenylene ether)-polysiloxane block copolymers further.
Daiamid composition prepared by 18. methods according to any one of claim 1-17.
19. 1 kinds of daiamid compositions, comprise the product of melt blending the following:
The polymeric amide of 40 to 60 weight percentage;
Poly-(phenylene ether) of 3 to 13 weight percentage;
The fire retardant of 12 to 18 weight percentage, comprises metal dialkyl phosphinates, melamine polyphosphate, and zinc borate;
The described polymeric amide of 0.1 to 2 weight percentage and the expanding material of described poly-(phenylene ether); With
The glass fibre of 20 to 40 weight percentage;
Wherein, all weight percentage are the gross weights based on described daiamid composition.
20. daiamid compositions according to claim 19,
Wherein, described polymeric amide comprises polymeric amide-6,6;
Wherein, described daiamid composition comprises the described polymeric amide of 45 to 55 weight percentage;
Wherein, described poly-(phenylene ether) comprises homopolymer or the multipolymer of the monomer being selected from the group be made up of the following: 2,6-xylenol, 2,3,6-TMP, and their combination;
Wherein, described daiamid composition comprises described poly-(phenylene ether) of 6 to 12 weight percentage;
Wherein, described fire retardant comprises the described metal dialkyl phosphinates of 6 to 13 weight percentage, the described melamine polyphosphate of 3 to 7 weight percentage, and the described zinc borate of 0.2 to 2 weight percentage; And
Wherein, described composition comprises the glass fibre of 20 to 30 weight percentage.
21. daiamid compositions according to claim 20, wherein, described poly-(phenylene ether) comprises poly-(phenylene ether)-polysiloxane block copolymers further.
22. 1 kinds of goods comprising the composition of the product comprising melt blending the following:
The polymeric amide of 40 to 60 weight percentage;
Poly-(phenylene ether) of 3 to 13 weight percentage;
The fire retardant of 12 to 18 weight percentage, comprises metal dialkyl phosphinates, melamine polyphosphate, and zinc borate;
The described polymeric amide of 0.1 to 2 weight percentage and the expanding material of described poly-(phenylene ether); With
The glass fibre of 20 to 40 weight percentage;
Wherein, all weight percentage are the gross weights based on described daiamid composition.
23. 1 kinds of methods reducing the metal dialkyl phosphinates content of retardant polyamide composition, comprising:
Based on the weight of described daiamid composition, melt blending comprises the component of the following, to form described daiamid composition:
Poly-(phenylene ether) masterbatch of 5 to 30 weight percentage,
First polymeric amide of 35 to 70 weight percentage,
The glass fibre of 15 to 40 weight percentage, and
The fire retardant comprising metal dialkyl phosphinates of 10 to 20 weight percentage;
Wherein, based on the weight of described poly-(phenylene ether) masterbatch, described poly-(phenylene ether) masterbatch is the product that melt blending comprises the component of the following:
Poly-(phenylene ether) of 35 to 97 weight percentage, and
Second polymeric amide of 3 to 65 weight percentage.
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